Water soluble aminoplast-ether copolymers

ABSTRACT

A linear aminoplast-ether copolymer of the formula: ##STR1## where the divalent R 01  contains a divalent alkyleneoxy containing moiety, Amp is the skeletal residue of an aminoplast, R is hydrogen, alkyl containing 1 to about 4 carbon atoms, and acyl containing 1 to about 4 carbon atoms, p is a positive number that is equal to the free valence of Amp minus 2, RO is bonded to alkylene units of Amp, and a is a number greater than 1. The method for making the copolymer is described.

BRIEF DESCRIPTION OF THE INVENTION

A water soluble linear aminoplast-ether copolymer containing aminoplastsegments interlinked through ether segments. These linear aminoplastethers are extremely desirable associate thickeners for use in waterbased coating compositions.

BACKGROUND TO THE INVENTION

Aminoplasts are defined herein and in the claims as an A-stage class ofthermosetting resin based on the reaction of an amine with an aldehydeand the related acetals containing amines or amides. The mostcommercially used aldehyde is formaldehyde, and the most importantamines are urea and melamine. They are used in molding, adhesives,laminating, textile finishes, permanent-press fabrics, wash-and-wearapparel fabrics, protective coatings, paper manufacture, leathertreatment, binders for fabrics, foundry sands, graphite resistors,plaster-of-paris fortification, foam structures, and ion-exchangeresins. A significant structural component of an aminoplast resin is theamino group to which is bonded at least one alkylol or alkylol ether orester functional group. Those functional groups enter into condensation(heterolytic) reactions and provide the leaving groups for the reaction.The aminoplast typically provides at least two of such amino groups permolecule and one or two functional groups per amino group. Thecondensation reaction can generate a low to moderate molecular weightpolymer (as would occur in making a B-stage resin), a highly crosslinkedpolymer (as would occur in making a thermoset C-stage resin) byhomopolymerization or copolymerization, or it can generate amodification of the resin that either provides other type functionalityor eliminates such functionality from the resin. For example, a startingmonomer that contains the amino group with an associated methylol ormethylol ether or ester group can be partially condensed and modifiedwith a monomer that possesses, in addition, different functionality(such as ethylenic unsaturation) and such partial modification allowsthe aminoplast to be dimerized, oligomerized or polymerized by ahomolytic reaction through such different functionality to formaminoplasts with a plethora of methylol and/or methylol ether and/orester groups. This same result can be achieved by different route, byhaving the skeleton of the aminoplast possess other functional groupsthat can enter into heterolytic or homolytic reactions. For example,methacrylamide can be reacted with formaldehyde to form an aminoplast,and through the unsaturation, polymerization can be effected to create alinear polymer with pendant methylol or methylol ether or esterfunctional groups. Illustrative of such aminoplasts are the following:##STR2## wherein R is hydrogen, alkyl containing 1 to about 4 carbonatoms, and acyl containing 1 to about 4 carbon atoms; R₀ is alkyl offrom 1 to about 4 carbon atoms, aryl, cycloalkyl, and the like; R₁ isalkyl of from 1 to about 4 carbon atoms; and x is 0 or 1, and y is atleast 2.

The RO-- functionality of such aminoplasts provide the leaving groups ofthe alkylol (e.g., methylol) or alkylol ether or ester (e.g., methylolether or ester) functional groups. Alkylol (e.g., methylol), alkylolether (e.g., methylol ether) or alkylol ester (e.g., methylol ester)groups can condense with them selves to form ROH volatile compounds orwater. They can condense with complementary functional groups, such ascompounds containing active hydrogen groups, e.g., primary and secondaryamines, carboxylic acids, alcohols, phenols, mercaptans, carboxamides(including amides from urea, thiourea), and the like.

Most aminoplasts contain a minor amount of dimer and oligomer products.These products are formed in the making of the aminoplast and representprecondensation between aminoplast monomers. The dimer and oligomerproducts contain substantially more --OR functionality than theaminoplast monomer.

As noted above, aminoplasts are used to form thermoset resin structures.Because they contain at least two RO-- functional groups, they are usedto react in systems that contain at least two complementary functionalgroups. Frequently, aminoplasts are added to resin formulations as oneof many components. In such embodiments, there are no perceptiblestep-wise reactions between the aminoplast and any other component ofthe formulation. In such situations, it is not feasible to determinewith any degree of accuracy as to which of the specific components ofthe formulation the aminoplast reacts.

The term "associative thickener" is art recognized to mean a nonionichydrophobically modified water-soluble polymer capable of interacting inaqueous solution with itself and with other species such as latexparticles. Typically they are made by polymerizing polyethylene oxideprepolymers with isocyanates. Mono-ols or diols with large aryl, alkyl,or aryl/alkyl groups are included to provide the hydrophobicmodification. They are described in a number of patents. Hoy et al.,U.S. Pat. No. 4,426,485, patented Jan. 17, 1984, broadly describes thesematerials as "a water-soluble, thermoplastic, organic polymer . . .having segments of bunched monovalent hydrophobic groups." This patent,in its "Description of the Prior Art," discusses a major segment of theprior art, and without endorsing the conclusions therein stated,reference is made to such description to offer a background to thisinvention.

The two Emmons et al. patents, U.S. Pat. No. 4,079,028 and U.S. Pat. No.4,155,892, patented Mar. 14, 1978 and May 22, 1979, respectively,describe polyurethane associative thickeners that contain hydrophobicgroups interconnected by hydrophilic polyether groups. The thickenersare nonionic.

There are a number of commercial associative thickeners based on thedescriptions of the Hoy et al. and Emmons et al. patents.

Background on the use of thickeners in waterborne polymer systems,including those embraced in the characterization of this invention isset forth in the extensive literature on the subject, such as U.S. Pat.Nos. 4,426,485, 4,155,892, 4,079,028; 3,035,004; 2,795,564; 2,875,166and 3,037,952, for example. The polymeric thickeners of this inventionare also suitable as substitutes for the polymeric thickeners in thepolymeric systems disclosed in U.S. Pat. Nos. 2,875,166 and 3,035,004and in Canadian Pat. No. 623,617.

For the purposes of this invention and the discussion of the prior art,the skeletal unit of the aminoplast is the structure of the aminoplastminus the RO-- leaving groups bonded to alkylene of the alkylol oralkylol ether or ester of the aminoplast, regardless of whether any ofthe RO-- groups are removed from the aminoplast. That skeletal unit isreferred to herein and in the claims as "Amp."

In the following description and in the claims hereof, the term "waterdispersible," as such relates to aminoplast containing compositions andprecursors to such compositions, that are water soluble or mechanicallydispersible in water in a stable particulate form. A stable particulateform is one that retains its chemical characteristics after an extendedperiod of time. It can be mechanically mixed in such particulate form inwater, for an extended period of time at normal ambient conditions.

The term "linear," when used herein and in the claims to characterize apolymer, relates to a polymer that is devoid of crosslinking orbranching that renders the polymer solid and cured. A "wholly linear"polymer is a polymer that is devoid of crosslinking and branching. Alinear polymer may or may not be a wholly linear polymer.

The symbols and designations used herein are intended to be consistentlyapplied, especially as used in formulations and equations, unlessspecifically stated otherwise.

THE INVENTION

This invention relates to aminoplast-ether copolymers formed by aprocess that does not rely on an urethane-forming polymerizationreaction in order to generate the copolymer's backbone structure.

This invention relates to a novel linear aminoplast-ether copolymer ofthe formula: ##STR3## where the divalent R₀₁ contains a divalentalkyleneoxy containing moiety, Amp is the skeletal residue of anaminoplast, as stated above, R is defined above, p is a positive numberthat is equal to the free valence of Amp minus 2, RO is bonded toalkylene units of Amp, and a is a number greater than 1, preferablygreater than 2. Amp includes any dimer and oligomer component of theaminoplast. In a much preferred embodiment of the invention, R₀₁ isderived from a water dispersible alkylene polyether, preferably a watersoluble alkylene polyether, and the novel linear aminoplast copolymer ofthe invention is water dispersible, and preferably, water soluble.

In addition, the invention relates to a novel linear aminoplast-etherco-polymer that contains one or more pendant groups, preferablyhydrophobic pendant groups. Such a copolymer contains a unit of theformula: ##STR4## wherein R₀₂ is a hydrophobic group, different fromRO--, that is covalently bonded to Amp through a heteroatom and containsat least two carbon atoms, preferably at least two sequential carbonatoms,

p₂ is number that is equal to the free valence of Amp minus (2+q), and

q is a positive number. The copolymer preferably contains a ratio of q/athat is at least about 0.01.

In another embodiment of the invention, the novel linearaminoplast-ether copolymer possesses end groups characterized by acomponent of the units making up the copolymer, or a monofunctionalgroup that effectively end-caps the copolymer, forming the end group.This yields a copolymer of the formula: ##STR5## wherein each R₀₀ is thesame or different terminal group, such as hydrogen, --R₀₁ --H, Ampbonded --(OR)_(p1), --Amp--(OR)_(p1), or any other monofunctionalorganic groups, such as alkyl, cycloalkyl, aryl, alkaryl, aralkyl,alkyoxyalkyl, aroxyalkyl, cycloalkoxyalkyl, and the like, and p₁ is apositive number that is equal to the free valence of Amp minus 1. Inaddition, the invention encompasses a copolymer of the formula: ##STR6##where each R₀₀₁ is the same or different, and is R₀₀ or R₀₂.

A preferred composition of the invention is the novel linearaminoplast-ether copolymer comprising units of the formula: ##STR7##wherein R₀₁ and R are described above, n has a value of at least 2, x is0 or 1, s is (3+x)-2, and the average value of x in the copolymer isabout 0 to about 0.05. Another preferred composition of the invention isa novel linear aminoplast-ether copolymer having the formula: ##STR8##where s+t equals (i) the free valence of the ##STR9## moiety and (ii)4-x; and the average value of t/s+t is about 0.01 to about 0.5.

In a further preferred embodiment of the invention, the novel linearaminoplast-ether copolymer of the invention comprises a copolymer thatpossesses end groups as illustrated by the following structure:##STR10## wherein each R₀₀₂ is the same or different terminal group,such as hydrogen, --R₀₁ --H, --(OR)_(p1), --Amp⁰ --(OR)_(p1), or anyother monofunctional organic groups, such as alkyl, cycloalkyl, aryl,alkaryl, aralkyl, alkyoxyalkyl, aroxyalkyl, cycloalkoxyalkyl, and thelike, and p₁ is a positive number that is equal to the free valence ofAmp⁰ minus 1. Amp⁰ is depicted in formula V. In a preferred embodimentof the invention, the novel linear aminoplast-ether copolymer of theinvention comprises a copolymer that possesses end groups affecting theperformance of the copolymer. Such embodiment is illustrated by thefollowing structure: ##STR11## wherein each R₀₀₃ is the same ordifferent terminal group, such as hydrogen, --R₀₁ --H, --(OR)_(p1),--Amp⁰ --(OR)_(p1), --R₀₂ or any other monofunctional organic groups,such as alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkyoxyalkyl,aroxyalkyl, cycloalkoxyalkyl, and the like, and p₁ is a positive numberthat is equal to the free valence of Amp⁰ minus 1. Amp⁰ has the samemeaning as Amp.

In the foregoing characterizations set forth in formulae I, Ia, II, IIa,III, IIIa, IV, and IVa, each --OR and --OR₀₂ group is directly bonded toAmp through a hydrocarbyl moiety bonded to nitrogen therein.

This invention also relates to aqueous systems that contain any one ormore of the above defined compositions. The invention relates to athickened water containing composition in which water is present in amajor amount and one or more of the aminoplast-based compositions offormulae I, Ia, II and IIa in a minor amount. Particularly preferred aresuch thickened water containing systems wherein the aminoplast-basedcompositions are the aminoplast-based compositions of formulae III,IIIa, IV and IVa. Particularly preferred water-based systems arecoating, adhesive, quenchant, flocculant, cosmetic, ink, textileprinting, paste, personal care product, cosmetics, hydraulic fluid, andthe like, compositions.

In addition, the invention relates to a water-based composition thatcontains a major amount of water, minor amount of an associativethickener of the formula: ##STR12## wherein R₀₃ is a monovalenthydrophobe as illustrated in the definition of R₀₂, and v has an averagevalue of about 2 to about 10,000, and an amount of a "dispersed polymer"that is greater than the amount of the associative thickener, whichdispersed polymer provides the basic utility for the composition. Inthis sense, the dispersed polymer is typically solvent dispersible,i.e., it has the capacity of being dissolved by a solvent, and on dryingthe composition, i.e., removing water and solvent present, the dispersedpolymer is curable to either a solid thermoset structure or a solidthermoplastic.

Another feature of the invention is the method for making the linearaminoplast-ether copolymer. The method comprises the copolymerizationreaction of a polyfunctional aminoplast with an ether containing twoactive hydrogen terminal groups, in the presence of an acid catalyst,especially a Bronsted-Lowery acid provided in catalytically effectiveamounts. The reaction is continued until the desired molecular weight isachieved. The desired molecular weight of the copolymer is dependent onthe intended use of the copolymer. The molecular weight of the copolymermay range from about 12,000 to about 300,000, preferably from about20,000 to about 100,000, and most preferably from about 30,000 to about80,000. The aminoplast is a polymerizable resin of the general formula:##STR13## wherein z is a positive number having a value of at least 2.The ether containing two active hydrogen terminal groups comprises awide variety of compositions. A preferred class of them is nonionic.Illustrative of a preferred class of such ethers are polyalkylene oxidesof the formula:

    H-- Alkylene Oxide --H                                     VIII.

where "alkylene oxide" is a divalent moiety containing at least twoalkylene oxide units in which

1. the alkylene oxide units form a linear chain and provide a terminalOH, or

2. the alkylene oxide are bonded to a starter molecule, such as adiamine, urea, carbamate, phenoxy, amide, bis-imide, and the like, andproviding a terminal OH, and/or

3. in which alkylene oxide are bonded to a terminal group that possessesa moiety that provides the active hydrogen (--H in formula VIII).

Further illustrative of such a preferred class are the water dispersiblepolyether compounds of the formula:

    H.sub.x1 X--(R.sub.04).sub.x4 (R.sub.05).sub.x5 (R.sub.06).sub.x6 (R.sub.07).sub.x7 (R.sub.08).sub.x8 --XH.sub.x2           IX.

wherein

X is an active hydrogen-attached functional moiety such as oxy (--O--),sulfidyl (--S--), amino (^(>N--)), carboxy (--COO--), carboxamido,silyl, phosphoryl, ureido, and the like;

R₀₄ and R₀₈ are alkyl of 2 to about 8 carbon atoms;

R₀₅ and R₀₇ are one or more alkylene oxide units, e.g., such as waterdispersible ethylene oxide, propylene oxide, mixed ethyleneoxide/1,2-propylene oxide, mixed ethylene oxide/1,3-propylene oxide,mixed ethylene oxide/1,2-butylene oxide, mixed ethyleneoxide/1,4-butylene oxide, and the like;

R₀₆ is a divalent group such as alkyleneoxy, alkylenepolyamine,cycloalkylene polyamine, phenoxy, uriedo, carbamate, amide, and thelike;

x1 and x2 are each equal to the free valence of X;

x3, x4, x5, x6 and x7 are each 0 or 1, and one or more of x4 and x6 is1.

Specific illustrations of a limited class of polyethers encompassed byformula IX are the Carbowax® and Pluronic® polyether diols sold by UnionCarbide Chemicals & Plastics, Inc. and BASF Wyandotte, respectively.There are a variety of functional fluids based on alkylene oxides thatare sold by Union Carbide Chemicals & Plastics, Inc. and BASF Wyandottethat are encompassed by formula IX. The molecular weight of thepolyether reagent may range from about 106 and lower, to about 35,000,and higher.

DETAILED DESCRIPTION OF THE INVENTION

The linear aminoplast-ether copolymers of formula I et seq. are made bythe novel condensation reaction of a polyfunctional aminoplast with adifunctional polyether (alone or with another polyol, as characterizedwith respect to formulae XII and XIII) in the presence of an acidcatalyst. In the prior art, as noted above, aminoplasts are condensedwith polyfunctional compounds to produce thermosetting resins orthermoset products (i.e., C-stage resin). The reaction of this inventionproduces a linear copolymer. Thus, the copolymers of formulae I, II,III, IV, and V are either liquid or thermoplastic solids that aresolvent soluble and water dispersible.

This invention converts aminoplast reagents to make associativethickener copolymers. Aminoplast reagents include, but are notrestricted to, aldehyde reaction products of melamines, ureas,benzoguanamines, glycolurils, and the like, to produce the array ofaminoplasts, including but not limited to those described in FIG. 1above. While any of these can be used to make associative thickeners,the glycolurils, such as those of formula X ##STR14## where R and x aredefined above, have shown appropriate hydrolytic stability, when reactedwith the polyether compounds, such as those encompassed by formula IX,to meet commercial criteria for associative thickener containing coatingcompositions. However, the reaction products of such aminoplasts with,e.g., thiols and NH groups from amides and carbamates, encompassed byformula IX, are much more hydrolytically stable than aminoplast etherlinkages. Reaction with more hindered hydroxyl groups aids in providinga more stable product. The use of such reactants allow for theproduction of most hydrolytically stable aminoplast-based copolymers.

Suitable polyethers include such diverse polyalkylene polyethers asthose having the formula: ##STR15## where x10 has a value of from about1 to about 400, R₁₂ are alkyl of 1 to about 4 carbon atoms or acyl of 1to about 3 carbon atoms. The preferred polyethers are water soluble. Themost preferred polyethers are the alkylene polyethers where thepredominant alkylene groups are ethylene. The most desirable polyethersare polyethylene oxide diols that possess molecular weights from about1,000 to about 20,000.

Illustrative of the desirable polyethylene oxide diols are those of theformula:

    HO--(--CH.sub.2 CH.sub.2 O).sub.x11 CH.sub.2 CH.sub.2 OH   XI.

wherein x11 has a value of about 20 to about 500, preferably from about50 to about 350, and most preferably from about 100 to about 250.

A further desirable embodiment of the invention is the modification ofthe linear aminoplast-ether copolymers of the invention by including aminor mole proportion of the following unit structure in the repeatingstructure of the copolymer:

    --Amp--R.sub.13 --                                         XII.

wherein R₁₃ is the residue of a diol possessing greater hydrophobicitythan R₀₁, thereby providing for a linear copolymer containing thestructure ##STR16## wherein x29 has a value that is greater than x30.Preferably, x30/x29 is less than about 1, preferably less than about0.33. Illustrative of such R₁₃ groups are ##STR17## wherein x31 has avalue of about 8 to about 20, x32 has a value of about 8 to about 23,x33 and x34 have values of 0 to about 8. The linear copolymer of formulaXIII may be modified to possess the terminal groups of formulae Ia, IIa,IIIa, and IVa, discussed above.

The invention encompasses the linear aminoplast-ether copolymersembraced by formulae I and XIII, that contain, as well, hydrophobependant groups. This is illustrated by the presence of significanthydrophobic groups extending from aminoplast component of the linearbackbone of the aminoplast-ether copolymer. Such hydrophobe groups aretypically bonded to the backbone through ether or ester groups, asillustrated in formula VI. The nature of the hydrophobe can enhance theperformance of the resulting aminoplast-ether copolymer as anassociative thickener. Aromatic groups, e.g., phenyl, biphenyl,anthracyl, and the like, present in the hydrophobes are better thanhydrophobes based on wholly aliphatic containing groups, especially forhigh shear viscosity attributes when used in water, and especially sowith respect to the use of the associative thickeners of the inventionin latex paints. Suitable hydrophobe groups are derived from alcohols,thiols, carboxylic acids, carboxamides, and carbamates of the formula:##STR18## wherein R₀₉ is hydrogen, alkyl of 8 to about 24 carbon atoms,alkenyl of 8 to about 24 carbon atoms and alkynyl of 8 to about 24carbon atoms, R₁₀ is mono, di and tri(aryl), R₁₁ is aryl, mono, di andtri(alkaryl), mono, di and tri(alkcycloalkyl), alkenyl and alkynyl wherethe alkyl, alkenyl and alkynyl contain 1 to about 24 carbon atoms andthe cycloalkyl contains about 4 to about 8 carbon atoms, R₁₂ is one ormore alkylene oxide, Y is an active hydrogen containing group such asOH, SH, COOH, CONHR₀₈, NR₀₉ COOH, x13, x14, x15 and x16 are 0 or 1, andtwo or more of x13, x14, x15 and x16 have the value of 1 at the sametime. Illustrative of such hydrophobe groups are the following precursorcompounds from which the hydrophobe is derived: ##STR19## where thederived hydrophobes are ##STR20## and in which R₁₄ is hydrogen or alkylof 1 to about 12 carbon atoms, R₁₅ is aryl or alkyl of 8 to 24 carbonatoms, x17 has a value of 7 to 23, x18 has a value of 1 to about 20, x19has a value of 0 to about 8, x20 is 0 or 1, x21 is 0 or 1, x22 has avalue of 1 to about 20, x23 has a value of 1 to about 23, x24 has avalue of 0 to about 120, x25 has a value of 1 to about 20, x26 has avalue of about 8 to about 60, and x27 is 0 or 1, the sum of x19 and x20is 1 to about 23, and the sum of x22 and x25 is 1 to about 20. Anotherclass of such hydrophobes are based on partially saponified fatty acidglycerides such as partially saponified linseed oil, tall oil,cottonseed oil, castor oil, coconut oil, corn oil, oiticica oil, perillaoil, poppyseed oil, rapeseed oil, and the like. A further class of suchhydrophobes are ethoxylates of such partially saponified fatty acidglycerides. Illustrative of such esters are ##STR21## where R₁₆ are thehydrocarbyl portion of the natural fatty acid component of the fattyacid glycerides. Their ethoxylates are illustrated as ##STR22## wherex28 has a value of 1 to about 200, and R₁₆ are the natural fatty acidcomponent of the natural oil.

The choice of hydrophobe is primarily dependent on the use ascribed forthe associative thickener of the invention. For example, the copolymerwithout the hydrophobe provides wetting agent and viscosity controlfeatures in water and with water-based compositions. In the demandingarea of water-based coatings, it is desirable to include a hydrophobe asa component of the aminoplast-ether copolymer of the invention. Any ofthe aforementioned hydrophobes will affect the viscosity of a latexpaint giving rise to benefits to the paint. However, certain of thehydrophobes in combination with certain of the aminoplast-ethercopolymers, provide associative thickeners that essentially satisfy themost demanding commercial standards. For example, the use ofdodecylphenol ethoxylates as the hydrophobe achieves particularlydesirable high shear viscosity characteristics, resistance to spatterand gloss retention in semi-gloss paints when compared to nonylphenoland octylphenol ethoxylates which have often been employed in makingassociative thickeners with urethane in the polymer backbone. It hasalso been observed that using tristyrylphenol ethoxylates improves thegloss of semi-gloss paints even further and provides better high shearresistance according to the ICI cone and plate viscometer reading inflat latex paints. Reacting Bisphenol A into the associative thickeners(to form the copolymer of formula XIII) reduces the syneresis commonwhen using associative thickeners in concert with cellulosics.

This invention relates to the use of any aminoplast, including thosespecifically recited in FIG. 1 above, to make the copolymer of theinvention. Of these aminoplasts, exceptionally performing associativethickeners are obtained from the reaction of glycolurils with alkyleneoxide glycols to form copolymers in which there are incorporatedhydrophobic pendant and/or terminal moieties.

The production of the aminoplast-ether copolymers of the invention aremade by solvent or melt polymerization. The typical preparation of anaminoplast-, such as glycoluril-, based associative thickener involvesdissolving the aminoplast (e.g., glycoluril), a polyether compoundswithin the scope of formula IX (such as a Carbowax® polyether sold byUnion Carbide Chemical and Plastics, Inc., Danbury, Conn.), with orwithout the addition of a more hydrophobic polyol within the scope offormula XII, and an ethoxylated hydrophobe, in a stripping solvent, suchas alkylated benzene (e.g., toluene or xylenes). Prior to thecombination of these reagent, each may be dried by azeotropicdistillation with toluene, xylenes, or a mixture of them, or by anyother drying procedure. Total concentration of the reagents in thesolvent may be maintained from about 10 to about 60 weight %. Thetemperature of the mixture may be brought to about 60-140° C.,preferably to about 80-120° C. An acid catalyst, such as a sulfonic acidcatalyst, is then added. The reaction mixture is placed under reducedpressure to bring about a steady distillation of the toluene/xyleneswhich azeotropes the alcohol byproduct that must be removed in order forthe reaction to proceed. Fresh solvent is constantly added to maintain aconstant level. The reaction is allowed to proceed until a given highviscosity is achieved as measured by Gardner bubble tubes or untilviscosity increase ceases. Such viscosity increase indicates an increasein the molecular weight of the copolymer.

SPECIFIC ILLUSTRATION OF SOLVENT PROCESS

1. Polyether polyol, hydrophobe and azeotroping solvent (e.g., toluene)are added to an appropriately sized container that accommodates aheater, temperature reading device, a nitrogen inlet, and a Dean Starkwater trap and condenser.

2. The mixture of step 1 is heated to reflux to dry the mixture byazeotropic distillation. When water removal ceases, the mixture iscooled to about 100° C., and the water trap is removed. A distillationcolumn and receiving vessel are installed.

3. Glycoluril (e.g., Powderlink 1174) is added and allowed to dissolve.

4. The catalyst is added and vacuum is applied. The pressure is reducedto a level that causes a steady distillation of solvent at about 100° C.The solvent is continually replenished from a pressure equalizing addfunnel.

5. As the reaction proceeds, samples are removed and cooled to roomtemperature, and the Gardner bubble viscosity is measured.

6. When the proper viscosity is reached, the heat is removed and themixture is cooled in a water bath. When the temperature has been reducedto below 75° C., an amine neutralizing agent is added. When thetemperature is reduced to below 65° C., the polymer solution is pouredout onto trays to air dry.

7. The dried polymer is cut into strips and redissolved in water orwater/cosolvent mixture.

Polymerization in the melt involves the admixture of the same reagentsin the absence of a solvent with a heavy duty laboratory mixer (such asan Universal Sigma Blade Mixer, sold by Baker Perkins Guittard SA,Paris, France) at a temperature sufficient to generate leaving groupsand remove the reaction condensation products. The ventilation of thereaction is necessary in order to shift the reaction to the right andprevent an equilibrium reaction from occurring that impedes the reactionbefore the desired degree of polymerization is achieved.

Catalysts useable for effecting the copolymerization reaction includesthe standard Bronsted-Lowery acid catalysts typically used for thecondensation of aminoplast resins. Such acid catalysts include mineralacids (e.g., HCl, H₂ SO₄, H₃ PO₄, and the like), aryl sulfonic andalkylated aryl sulfonic acids, such as benzene sulfonic acid, p-toluenesulfonic acid, 1-naphthalene sulfonic acid, 2-naphthalene sulfonic acid,naphthalene-1,5-disulfonic acid, naphthalene-2,7-disulfonic acid,1,3,6-naphthalene trisulfonic acid, naphtholsulfonic acid,dinonylnaphthalene disulfonic acid, dodecylbenzene sulfonic acid, oxalicacid, maleic acid, hexamic acid, alkyl phosphate ester, phthalic acid,and copolymerized acrylic acid. Of these catalysts, the sulfonic acidcatalysts are the most effective and efficient for making the copolymersof the invention and dodecylbenzene sulfonic acid is the most preferredsulfonic acid catalyst.

Glycolurils are marketed by Cytec Industries as Cymel 1170, 1171, 1175and Powderlink 1174. The Cymel typically contain a relatively highdimer/oligomer content of up to about 20 weight percent. Powderlink 1174is a purer form that is solely the methyl ether of the formula:##STR23## with about 3-5 weight percent of a dimer-oligomer of themonomer form. The purer the monomeric form of the aminoplast, the betterit is in forming the copolymers of the invention. In about 5-7 weightpercent of Powderlink 1174, x is 0, and such monomer form istrifunctional. The dimer-oligomer forms provide greater amounts ofmethoxy per molecule. For example, the dimer contains 6 methoxyfunctional groups. Such tri- and hexa-functionality does not alter thisinvention. The glycoluril ether linkage is much more resistant tohydrolysis than other aminoplast ether bonds. The higher dimer-oligomercontent of the less pure glycolurils is not as favored as the lowerdimeroligomer content of Powderlink 1174.¹

The ratio of aminoplast resin to the difunctional polyether is notnarrowly critical. Typically, either the aminoplast resin or thedifunctional polyether may be used in molar excess or stoichiometricallyequivalent amounts in making the linear copolymer of the invention. Incharacterizing stoichiometry of the aminoplast resin, the resin istreated as being difunctional since linearity, according to theinvention, is achieved when the aminoplast resin functions as adifunctional monomer even though the resin has the capability of higherfunctionality, e.g., tri- and tetrafunctionality, as the case may be.Thus, more than one mole of a polyether diol to one mole of, e.g., aglycoluril such as Powderlink 1174, represents a stoichiometric excessof the polyether to the glycoluril. Using this characterization, one mayuse between 1-2 moles of one of these reagents to 1 mole of the other.Either the polyether or the aminoplast may be in excess. However, it ismore typical to use a mole amount of one reagent of about 1-1.75 to 1 ofthe other reagent. Typically, one employs a molar excess of theaminoplast resin because one may incorporate more hydrophobicity intothe copolymer this way. This is especially the case when the copolymeris dimeric to oligomeric (e.g., possessing less than about 15 repeatingunits). When making higher polymeric structures, one uses a greaterproportion of the polyether reagent, up to a 1:1 mole ratio. In general,it is desirable to use a molar excess of aminoplast of about 1.001-1.5moles to 1 mole of the difunctional polyether. The amount ofmonofunctional hydrophobe reagent, in the typical case, should notexceed about 2 moles, nor be less than about 0.001 mole, of themonofunctional hydrophobe per mole of reacted aminoplast resin in thecopolymer of the invention. Usually, the amount of monofunctionalhydrophobe ranges from about 1 mole to about 0.01 mole per mole ofreacted aminoplast.

The use of aminoplast reagents leads to an unexpected degree offormulating latitude in polymer synthesis. By varying the ratios ofpolyether and hydrophobe components, it is possible to make a largenumber of associative thickener copolymers that impart ICI viscosity of1.2 poise in flat paint at 4.5 lb. loading, but which give a range of15,000 to 75,000 centipoise at low shear. This latitude permits thefacile tailoring of associative thickeners for a wide variety of paintand nonpaint applications.

The associative thickeners of the invention are particularly suitablefor use in waterborne coating compositions. Waterborne coatings may bedefined as coatings that contain water as the major volatile componentand utilize water to dilute the coating to application consistency.These coatings consist mainly of resinous binder, pigments, water, andorganic solvent. The type of pigmentation and the method ofincorporation of the pigment vary widely.

Waterborne coatings can be made by dispersing, emulsifying or emulsionpolymerizing the resin binder by use of added surfactants. Thistechnique leads to opaque liquids. Because some hard resins aredifficult or impossible to disperse directly into water, the resinsometimes can be dissolved in a water-immiscible solvent, and theresulting solution dispersed by the use of added surfactants. In thiscase, the solvent aids subsequent film coalescence. Surface activity orwater dispersability also can be introduced into resin molecules bychemical modification of the resin by introducing functional polargroups such as the carboxyl group.

Some very finely dispersed resins appear as clear or slightly hazyliquids; they frequently are described as soluble, solubilized,colloidal dispersions, micro-emulsions, hydrosols, etc. These resinscontain built-in functional groups that confer water "solubility" uponthe resin, and, normally, external added surfactants are not used.

Waterborne resin binders can be classified as anionic, cationic, ornon-ionic. Anionic dispersions are characterized by negative charges onthe resin or by negative charges on the surfactant associated with theresin. Cationic dispersions have a positive charge on the resin or onthe surfactant associated with the resin. Nonionic dispersions are thosethat have been dispersed by addition of nonionic surfactants or thatcontain a built-in hydrophilic segment such as polyethylene oxide whichis part of the main chain of a relatively hydrophobic resin molecule.

The coating compositions may be of the thermosetting or thermoplasticvarieties. The resin used in forming the coating may be insoluble inwater, and the conversion of such a resin into a waterborne systemtypically involves converting the resin into an emulsion or dispersion.In the context of this invention, the waterborne composition containsthe aminoplast-ether copolymer associative thickener of the invention.

The aqueous polymer dispersions may be prepared according to well knownemulsion polymerization procedures, using one or more emulsifiers of ananionic, cationic, or nonionic type. Mixtures of two or morenonneutralizing emulsifiers regardless of type may be used. The amountof emulsifier may range from about 0.1 to 10% by weight or sometimeseven more, based on the weight of the total monomer charge. In general,the molecular weight of these emulsion polymers is high, e.g., fromabout 100,000 to 10,000,000 number average molecular weight, mostcommonly above 500,000.

The water insoluble resin may be any of those known in the art, and maybe a conventional natural or synthetic polymer latex emulsified with oneof a nonionic, cationic or anionic surfactant. The primary resins arebased on homopolymerized and copolymerized olefinic monomers such asvinyl acetate; vinyl chloride; styrene; butadiene; vinylidene chloride;acrylonitrile; methacrylonitrile; acrylic acid; methacrylic acid; alkylacrylates; alkyl methacrylates; acrylamide; methacrylamide; hydroxyethylmethacrylate ("HEMA"); glycidyl methacrylate; dihydroxypropylmethacrylate; homopolymers of C₂ -C₄₀ alpha-olefins such as ethylene,isobutylene, octene, nonene, and styrene, and the like; copolymers ofone or more of these hydrocarbons with one or more esters, nitriles oramides of acrylic acid or of methacrylic acid or with vinyl esters, suchas vinyl acetate and vinyl chloride, or with vinylidene chloride; anddiene polymers, such as copolymers of butadiene with one or more ofstyrene, vinyl toluene, acrylonitrile, methacrylonitrile, and esters ofacrylic acid or methacrylic acid, and the like. It is also quite commonto include a small amount, such as 0.1 to 5% or more, of an acid monomerin the monomer mixture used for making the copolymers mentioned above byemulsion polymerization. Acids used include acrylic, methacrylic,itaconic, crotonic, maleic, fumaric, and the like.

The vinyl acetate copolymers are well-known and include copolymers suchas vinyl acetate/butyl acrylate/2-ethylhexyl acrylate, vinylacetate/butyl maleate, vinyl acetate/ethylene, vinyl acetate/vinylchloride/butyl acrylate and vinyl acetate/vinyl chloride/ethylene.

Other waterborne systems involve reactive copolymers that arecrosslinked by the presence of complementary functional groups in thesystem. For example, a copolymer of acrylic ester/glycidylmethacrylatecan be emulsified and crosslinked by the presence of amelamine-formaldehyde resin similarly emulsified in the system. Inanother system, a copolymer of HEMA and another acrylate, hydroxylterminated polyesters, polyethers, or polyurethanes, can be emulsifiedand crosslinked by the presence of either an aminoplast resin, apolyisocyanate or blocked polyisocyanate.

The term "acrylic polymer" means any polymer wherein at least 50% byweight is an acrylic or methacrylic acid or ester, including mixtures ofsuch acids and esters individually and together. The term "vinyl acetatepolymer" means any polymer containing at least 50% by weight of vinylacetate.

Even small particle size (about 0.1-0.15 micron) acrylic and otherlatices are thickened effectively, and flow and leveling improved, bythickeners of the invention.

EXAMPLE 1

Carbowax® 8000² (300 grams, 0.0357 moles), Igepal RC-620³ (23.0 grams,0.0338 moles), a mixture of dodecylphenolethoxylates, were combined with1356 grams toluene in a 2 liter reaction vessel fitted with a Dean Starkwater trap. The mixture was refluxed under nitrogen to remove water byazeotropic distillation. The Dean Stark trap was removed, and adistillation column was fitted to the flask. Powderlink 1174 (15.92grams, 0.050 moles) was added and the temperature was raised to 100° C.and Nacure 5076⁴ (1.38 grams) (dodecylbenzene sulfonic acid) was added.Vacuum was applied to reduce the pressure inside the vessel toapproximately 510 mm Hg. At this pressure the toluene distilled at aslow, steady rate. The toluene was constantly replenished to maintain aconstant solvent level. This proceeded for 125 minutes at which time theviscosity was "X" on the Gardner bubble scale. The copolymer solutionwas cooled to 70° C. and dimethylethanolamine (0.53 gram) was added toquench the acid. The copolymer solution was cooled further to 60° C. andthen poured out onto trays to air dry. The dried polymer was cut intosmall pieces and was dissolved at 20% polymer solids in a 4/1water-diethylene glycol monobutyl ether mixture.

EXAMPLE 2 Procedure For Making Associative Thickeners Without Solvent

Carbowax 8000 (2204 grams, 0.262 moles) Igepal RC620 (168.9 grams, 0.248moles), and 500 grams of toluene were placed in a 12 liter vesselequipped with a Dean Stark water trap. The materials were heated toreflux to azeotrope off water. Once the mixture was dry the remainder ofthe toluene was removed with vacuum. Powderlink 1174 (117.0 grams, 0.367moles) was added and allowed to melt out. After the Powderlink hadmelted the material in the vessel was transferred to a a liter sigmablade mixer pre-heated to 105° C. The mixer was turned to run at 20 rpm.Nacure 5076 catalyst (7.10 grams) was added and the top was placed onthe mixer. Vacuum was applied (27/30 in. achieved) and held for 1.75hours as the viscosity increased. When the material had become quiteviscous the heat was removed and dimethylethanolamine (3.87 grams, 0.043mole) in 10 grams of toluene was added and the mixture was allowed tostir for a further 30 minutes. Diethyleneglycol monobutyl ether (1850grams) and deionized water (7200 grams) were added and the mixture wasallowed to stir until the material had dissolved. The resulting solutionwas filtered through a cone filter. Paint results are as follows:

    ______________________________________    flat vinyl acrylic semi-gloss vinyl acrylic:    (formulation below):                       (formulation below):    ______________________________________    ICI:1.05 poise     ICI:0.90 poise    Stormer: 104 KU    Stormer: 78 KU    Brookfield: 49,000 cps                       Brookfield: 8,000 cps    ______________________________________

EXAMPLE 3

Using the procedure of Example 1, with the indicated modifications, thefollowing other aminoplast-ether copolymers were made:

    ______________________________________    Aminoplast-ether copolymer formulatlon    Reagent              Concentration    ______________________________________    Cymel 1171 (mixed ether glycoluril).sup.5                        0.0628         moles    Carbowax 8000       0.0349         moles    Tergitol NP-10.sup.6                        0.0489         moles    p-Toluene sulfonic acid                        0.53           grams    toluene             1412           grams    ______________________________________     .sup.5 Cytec Industries, Inc.     .sup.6 Ethoxylated nonyl phenol, sold by Union Carbide Chemical &     Plastics, Inc.

Conditions: The maximum reaction temperature was 100° C. The reactionwas carried out at atmospheric pressure (no vacuum pulled). The Gardnerscale was used in monitoring viscosity.

    ______________________________________    Reagent                 Concentration    ______________________________________    Cymel 303 (hexamethoxymethylmelamine).sup.7                           0.070        moles    Carbowax 8000          0.047        moles    Tergitol NP-10         0.052        moles    p-Toluene sulfonic acid                           0.94         grams    toluene                1,665        grams    ______________________________________

Conditions: The maximum reaction temperature was 100° C. The reactionwas carried out at atmospheric pressure (no vacuum pulled). The Gardnerscale was used in monitoring viscosity.

Evaluation in Semi-Gloss Latex Paint Formulation

The 20% solution of example 1 was evaluated in a semi-gloss trade paintformulation, which consisted of a 24.4% PVC system using UCAR 376vinyl-acrylic latex with Ti-Pure R-900 TiO₂. Listed below are therheological and application results for example 1 and two commercialnonionic associative thickeners.

    ______________________________________               Loading, Brook-               active   field    Associative               lbs/100  cps @   Stormer                                      ICI       60°    Thickeners gallons  0.5 rpm KU    poise                                           Sag  gloss    ______________________________________    Example 1  5.0       9,720  85    1.00 10.0 45    Acrysol SCT-270.sup.8               5.0      13,200  95    1.22 13.6 59    Acrysol RM-825.sup.9               5.0       2,640  85    1.14  6.8 37    ______________________________________     .sup.7 Cytec Industries, Inc.     .sup.8 Rohm & Haas Company, Philadelphia, PA     .sup.9 Rohm & Haas Company, Philadelphia, PA

    ______________________________________    Evaluation In Flat Latex Paint Formulation              Loading,              active    Associative              lbs/100  Brookfield Stormer                                        ICI  Spatter    Thickeners              gallons  cps @ 0.5 rpm                                  KU    poise                                             amount    ______________________________________    Example 1 4.5      36,240     106   1.22 trace    Acrysol SCT-270              4.5      59,600     118   1.40 nil    Acrysol RM-825              4.5      10,000      95   1.25 trace    ______________________________________

Procedure For Making and Testing Latex Paint Using Aminoplast BasedAssociative Thickeners

The following are the two primary formulations for evaluating aminoplastbased associative thickeners. One is of a flat vinyl acrylic and theother is a semi-gloss vinyl acrylic. Typically both formulations aremade in 5 gallon batches that are split into pints after the grind andlet-down stage, but prior to the addition of the premix which containsthe associative thickener.

The premix is added while the paint is being well agitated to ensurethat the associative thickener is well incorporated into the paint. Thepaint is then allowed to sit at rest for 60 minutes to allow thematerial to further equilibrate followed by rheological measurementswhich involve

1. viscosity measurement in Krebs Units (KU) on a Stormer viscometer(ASTM D 562-81)

2. high shear measurement in poise at 10,000 s⁻¹ on an ICI cone andplate viscometer (ASTM D 4287-83)

3. pH and temperature measurements are obtained.

The paints are maintained at room temperature (˜23.5° C.) and areevaluated as above at 24 hours, 1 week, 1, 2, 3, 6, and 12 months withthe following additions:

1. a syneresis measurement is obtained by determining the amount inmillimeters of the clear liquid that may separate to the top of thepaint

2. a low shear measurement is obtained in centipoise (cps) at 0.5 rpm ona Brookfield RVT viscometer (ASTM D 2196-86).

After the 24 hour rheological measurements the flat paints are evaluatedfor spatter resistance according to ASTM procedure D 4707-87 with theexception that the paints are rated by the amount of spatter producedfrom nil, trace, slight, definite and pronounced. After the 24 hourTheological measurements the semi-gloss paints are evaluated for glossat 60° C. after 1 day and 1 week room temperature air dry of a 0.004 mildraw down. Also the semi-gloss paints are evaluated for sag and levelingaccording to ASTM procedures D 4400-84 and D 2801-69.

The hydrolytic stability of the associative thickeners are determined bysubjecting the paints to an elevated temperature (48.9° C.) for 4 weekswith rheological measurements obtained at 1 week intervals. Theassociative thickeners are determined to be stable if the Stormerviscosity does not lose more than 10% of the initial value.

Procedure For Making Latex Paint

1. Add water (and propylene glycol for semi-gloss) to 5-galloncontainer, begin agitation on a Hockmeyer Model Lab 2 type disperserequipped with a 4 inch dispersing blade.

2. Add HEC for the flat formulation and let mix agitate 5 minutes at lowspeed (˜1000 rpm).

3. Add dispersant and mix 5 minutes, add other additives and pigment(s)and grind at high speed (˜2000 rpm) for the specified time.

4. For the semi-gloss formulation prepare a premix in a separatecontainer consisting of the water, HEC and ammonia, ensuring that theHEC is well dispersed in the water prior to the addition of the ammonia.

5. Add remaining let-down ingredients and agitate for 40 minutes, checkweight per gallon and pH, divide into pint containers.

    ______________________________________    Flat vinyl acrylic    Grind Stage Supplier         Pounds  Gallons    ______________________________________    Water                        170.94  20.52    Cellosize ER-15K                Union Carbide    1.00    0.09    (HEC thickener)   Mix HEC 5 minutes at low speed.    Tamol 731 (dispersant)                Rohm & Haas      10.50   1.14    Proxel GXL (preserva-                Zeneca Biocides  1.00    0.10    tive)    Colloids 643                Rhone-Poulenc    2.00    0.26    (defoamer)    AMP-95 (Co- Angus Chemical   1.00    0.13    dispersant)    Tergitol NP-10                Rohm & Haas      1.00    0.11    (Nonionic surfactant)    TI-Pure R-901 (TiO.sub.2                DuPont           200.00  6.40    Primary Hiding    Pigment)                   Grind TiO.sub.2  @ high speed 20 minutes    ASP-400 (Aluminum                Minerals & Chemicals                                 125.0   5.82    Silicate extender    pigment)    Duramite CaCO.sub.3                Thompson, Weinman & Co.                                 201.2   8.91    (extender pigment) Grind @ high speed 20 minutes                   Record maximum grind temperature    Let Down    Water                        50.00   6.00    UCAR 376 (Vinyl-                Union Carbide    271.5   30.00    acrylic latex 55%    solids)    Texanol (Coalescing                Eastman Chemical 7.90    1.00    Agent)    Ammonia (pH ad-                Aldrich          1.00    0.12    justing agent)                Sub total:       1044.04                      Mix at low speed 30 minutes                         Weight/Gallon 12.95                             Record pH:               Remove and divide into pints (522 grams/pint)    Premix:    Propylene glycol                Chemcentral      18.60   2.15    (freeze thaw agent)    Water                        117.70  14.13    Associative thickener                Example 1 above  22.50   2.60    at 20% solids    Colloids 643                Rhone-Poulenc    4.00    0.52    (defoamer)  Total:           1206.84 100.00                  Pigment volume concentration % 55.34                        Volume Solids % 38.19    ______________________________________

    ______________________________________    Semi-gloss vinyl acrylic    Grind Stage     Supplier     Pounds  Gallons    ______________________________________    Water                        9.58    1.15    Propylene glycol                    Chemocentral 60.00   6.94    Tamol 731 (dispersant)                    Rohm & Haas  10.20   1.11    Colloids 643 (defoamer)                    Rhone Poulenc                                 1.25    0.16    Ti-Pure R-900 (TiO.sub.2                    DuPont       255.00  7.66    Hiding Pigment)                  Grind TiO.sub.2  @ high speed 30 minutes;                   record maximum grind temperature:    Let Down    Water                        130.00  15.61    Cellocize ER-15,000 (HEC     1.00    0.09    thickener)           Premix water and HEC, add ammonia, agitate 10 minutes    UCAR 376 (Vinyl-acrylic latex                    Union Carbide                                 417.00  46.08    55% solids)    Ammonia                      2.00    0.24    Texanol (Coalescing Agent)                    Eastman Chemical                                 11.50   1.45    Triton GR-7M (Anionic                    Rohm & Haas  1.00    0.12    surfactant)    Colloids 643 (defoamer)                    Rhone Poulenc                                 1.25    0.16    Nuosept 95 (biocide)                    Huls America 3.00    0.33                    Sub Total    902.78                      Mix at low speed 30 minutes    Premix:    Water                        129.80  15.58    Triton x 114 (nonionic                    Rohm & Haas  1.00    0.11    surfactant)    Associative Thickener at                    Example 1 above                                 25.00   2.89    20% solids    Coloids 643 (defoamer)                    Rhone Poulenc                                 2.50    0.33                    Total:       1061.08 100.00                  Pigment volume concentration %: 23.19                        Volume solids %: 33.03    ______________________________________

We claim:
 1. A linear aminoplast-ether copolymer of the formula:##STR24## where the divalent R₀₁ contains a divalent alkyleneoxycontaining moiety, Amp is the skeletal residue of an aminoplast, R ishydrogen, alkyl containing 1 to about 4 carbon atoms, or acyl containing1 to about 4 carbon atoms, p is a positive number that is equal to thefree valence of Amp minus 2, RO is bonded to alkylene units of Amp, anda is a number greater than 1, in the presence of an acid catalyst. 2.The linear aminoplast-ether copolymer of claim 1 wherein a is a numbergreater than
 2. 3. The linear aminoplast-ether copolymer of claim 1wherein Amp includes any dimer and oligomer component of the aminoplast.4. The linear aminoplast-ether copolymer of claim 1 wherein R₀₁ isderived from a water dispersible alkylene polyether.
 5. The linearaminoplast-ether copolymer of claim 4 wherein R₀₁ is derived from awater soluble alkylene polyether.
 6. The linear aminoplast-ethercopolymer of claim 1 wherein the linear aminoplast-ether copolymer iswater dispersible.
 7. The linear aminoplast-ether copolymer of claim 2wherein the linear aminoplast-ether copolymer is water dispersible. 8.The linear aminoplast-ether copolymer of claim 3 wherein the linearaminoplast-ether copolymer is water dispersible.
 9. The linearaminoplast-ether copolymer of claim 4 wherein the linearaminoplast-ether copolymer is water dispersible.
 10. The linearaminoplast-ether copolymer of claim 5 wherein the linearaminoplast-ether copolymer is water dispersible.
 11. The linearaminoplast-ether copolymer of claim 6 wherein the linearaminoplast-ether copolymer is water soluble.
 12. The linearaminoplast-ether copolymer of claim 7 wherein the linearaminoplast-ether copolymer is water soluble.
 13. The linearaminoplast-ether copolymer of claim 8 wherein the linearaminoplast-ether copolymer is water soluble.
 14. The linearaminoplast-ether copolymer of claim 9 wherein the linearaminoplast-ether copolymer is water soluble.
 15. The linearaminoplast-ether copolymer of claim 10 wherein the linearaminoplast-ether copolymer is water soluble.
 16. The linearaminoplast-ether copolymer of claim 1 wherein the linearaminoplast-ether copolymer contains one or more pendant groups.
 17. Thelinear aminoplast-ether copolymer of claim 16 wherein the pendant groupsare hydrophobic pendant groups.
 18. The linear aminoplast-ethercopolymer of claim 17 wherein the copolymer contains a unit of theformula: ##STR25## wherein R₀₂ is a hydrophobic group, different fromRO--, that is covalently bonded to Amp through a heteroatom and containsat least two carbon atoms,p₂ is number that is equal to the free valenceof Amp minus (2+q), and q is a positive number.
 19. The linearaminoplast-ether copolymer of claim 18 wherein R₀₂ contains at least twosequential carbon atoms.
 20. The linear aminoplast-ether copolymer ofclaim 19 wherein the ratio of q/a is at least about 0.01.
 21. The linearaminoplast-ether copolymer of claim 18 wherein the ratio of q/a is atleast about 0.01.
 22. The linear aminoplast-ether copolymer of claim 1wherein the linear aminoplast-ether copolymer comprises units of theformula: ##STR26## wherein n has a value of at least 2, x is 0 or 1, sis (3+x)-2, and the average value of x in the copolymer is about 0 toabout 0.05.
 23. The linear aminoplast-ether copolymer of claim 4 whereinthe linear aminoplast-ether copolymer comprises units of the formula:##STR27## wherein n has a value of at least 2, x is 0 or 1, s is(3+x)-2, and the average value of x in the copolymer is about 0 to about0.05.
 24. The linear aminoplast-ether copolymer of claim 2 wherein thelinear aminoplast-ether copolymer comprises units of the formula:##STR28## wherein n has a value of at least 2, x is 0 or 1, s is(3+x)-2, and the average value of x in the copolymer is about 0 to about0.05.
 25. The linear aminoplast-ether copolymer of claim 3 wherein thelinear aminoplast-ether copolymer comprises units of the formula:##STR29## wherein n has a value of at least 2, x is 0 or 1, s is(3+x)-2, and the average value of x in the copolymer is about 0 to about0.05.
 26. The linear aminoplast-ether copolymer of claim 5 wherein thelinear aminoplast-ether copolymer comprises units of the formula:##STR30## wherein n has a value of at least 2, x is 0 or 1, s is(3+x)-2, and the average value of x in the copolymer is about 0 to about0.05.
 27. The linear aminoplast-ether copolymer of claim 6 wherein thelinear aminoplast-ether copolymer comprises units of the formula:##STR31## wherein n has a value of at least 2, x is 0 or 1, s is(3+x)-2, and the average value of x in the copolymer is about 0 to about0.05.
 28. The linear aminoplast-ether copolymer of claim 7 wherein thelinear aminoplast-ether copolymer comprises units of the formula:##STR32## wherein n has a value of at least 2, x is 0 or 1, s is(3+x)-2, and the average value of x in the copolymer is about 0 to about0.05.
 29. The linear aminoplast-ether copolymer of claim 8 wherein thelinear aminoplast-ether copolymer comprises units of the formula:##STR33## wherein n has a value of at least 2, x is 0 or 1, s is(3+x)-2, and the average value of x in the copolymer is about 0 to about0.05.
 30. The linear aminoplast-ether copolymer of claim 9 wherein thelinear aminoplast-ether copolymer comprises units of the formula:##STR34## wherein n has a value of at least 2, x is 0 or 1, s is(3+x)-2, and the average value of x in the copolymer is about 0 to about0.05.
 31. The linear aminoplast-ether copolymer of claim 10 wherein thelinear aminoplast-ether copolymer comprises units of the formula:##STR35## wherein n has a value of at least 2, x is 0 or 1, s is(3+x)-2, and the average value of x in the copolymer is about 0 to about0.05.
 32. The linear aminoplast-ether copolymer of claim 11 wherein thelinear aminoplast-ether copolymer comprises units of the formula:##STR36## wherein n has a value of at least 2, x is 0 or 1, s is(3+x)-2, and the average value of x in the copolymer is about 0 to about0.05.
 33. The linear aminoplast-ether copolymer of claim 12 wherein thelinear aminoplast-ether copolymer comprises units of the formula:##STR37## wherein n has a value of at least 2, x is 0 or 1, s is(3+x)-2, and the average value of x in the copolymer is about 0 to about0.05.
 34. The linear aminoplast-ether copolymer of claim 13 wherein thelinear aminoplast-ether copolymer comprises units of the formula:##STR38## wherein n has a value of at least 2, x is 0 or 1, s is(3+x)-2, and the average value of x in the copolymer is about 0 to about0.05.
 35. The linear aminoplast-ether copolymer of claim 14 wherein thelinear aminoplast-ether copolymer comprises units of the formula:##STR39## wherein n has a value of at least 2, x is 0 or 1, s is(3+x)-2, and the average value of x in the copolymer is about 0 to about0.05.
 36. The linear aminoplast-ether copolymer of claim 15 wherein thelinear aminoplast-ether copolymer comprises units of the formula:##STR40## wherein n has a value of at least 2, x is 0 or 1, s is(3+x)-2, and the average value of x in the copolymer is about 0 to about0.05.
 37. The linear aminoplast-ether copolymer of claim 16 wherein thelinear aminoplast-ether copolymer comprises units of the formula:##STR41## wherein n has a value of at least 2, x is 0 or 1, s is(3+x)-2, and the average value of x in the copolymer is about 0 to about0.05.
 38. The linear aminoplast-ether copolymer of claim 17 wherein thelinear aminoplast-ether copolymer comprises units of the formula:##STR42## wherein n has a value of at least 2, x is 0 or 1, s is(3+x)-2, and the average value of x in the copolymer is about 0 to about0.05.
 39. The linear aminoplast-ether copolymer of claim 22 wherein thecopolymer has the formula: ##STR43## where s+t equals (i) the freevalence of the ##STR44## moiety and (ii) 4-x; and the average value oft/s+t is about 0.01 to about 0.5.
 40. The linear aminoplast-ethercopolymer of claim 23 wherein the copolymer has the formula: ##STR45##where s+t equals (i) the free valence of the ##STR46## moiety and (ii)4-x; and the average value of t/s+t is about 0.01 to about 0.5.
 41. Thelinear aminoplast-ether copolymer of claim 24 wherein the copolymer hasthe formula: ##STR47## where s+t equals (i) the free valence of the##STR48## moiety and (ii) 4-x; and the average value of t/s+t is about0.01 to about 0.5.
 42. The linear aminoplast-ether copolymer of claim 25wherein the copolymer has the formula: ##STR49## where s+t equals (i)the free valence of the ##STR50## moiety and (ii) 4-x; and the averagevalue of t/s+t is about 0.01 to about 0.5.
 43. The linearaminoplast-ether copolymer of claim 26 wherein the copolymer has theformula: ##STR51## where s+t equals (i) the free valence of the##STR52## moiety and (ii) 4-x; and the average value of t/s+t is about0.01 to about 0.5.
 44. The linear aminoplast-ether copolymer of claim 27wherein the copolymer has the formula: ##STR53## where s+t equals (i)the free valence of the ##STR54## moiety and (ii) 4-x; and the averagevalue of t/s+t is about 0.01 to about 0.5.
 45. The linearaminoplast-ether copolymer of claim 28 wherein the copolymer has theformula: ##STR55## where s+t equals (i) the free valence of the##STR56## moiety and (ii) 4-x; and the average value of t/s+t is about0.01 to about 0.5.
 46. The linear aminoplast-ether copolymer of claim 29wherein the copolymer has the formula: ##STR57## where s+t equals (i)the free valence of the ##STR58## moiety and (ii) 4-x; and the averagevalue of t/s+t is about 0.01 to about 0.5.
 47. The linearaminoplast-ether copolymer of claim 30 wherein the copolymer has theformula: ##STR59## where s+t equals (i) the free valence of the##STR60## moiety and (ii) 4-x; and the average value of t/s+t is about0.01 to about 0.5.
 48. The linear aminoplast-ether copolymer of claim 31wherein the copolymer has the formula: ##STR61## where s+t equals (i)the free valence of the ##STR62## moiety and (ii) 4-x; and the averagevalue of t/s+t is about 0.01 to about 0.5.
 49. The linearaminoplast-ether copolymer of claim 32 wherein the copolymer has theformula: ##STR63## where s+t equals (i) the free valence of the##STR64## moiety and (ii) 4-x; and the average value of t/s+t is about0.01 to about 0.5.
 50. The linear aminoplast-ether copolymer of claim 33wherein the copolymer has the formula: ##STR65## where s+t equals (i)the free valence of the ##STR66## moiety and (ii) 4-x; and the averagevalue of t/s+t is about 0.01 to about 0.5.
 51. The linearaminoplast-ether copolymer of claim 34 wherein the copolymer has theformula: ##STR67## where s+t equals (i) the free valence of the##STR68## moiety and (ii) 4-x; and the average value of t/s+t is about0.01 to about 0.5.
 52. The linear aminoplast-ether copolymer of claim 35wherein the copolymer has the formula: ##STR69## where s+t equals (i)the free valence of the ##STR70## moiety and (ii) 4-x; and the averagevalue of t/s+t is about 0.01 to about 0.5.
 53. The linearaminoplast-ether copolymer of claim 36 wherein the copolymer has theformula: ##STR71## where s+t equals (i) the free valence of the##STR72## moiety and (ii) 4-x; and the average value of t/s+t is about0.01 to about 0.5.
 54. The linear aminoplast-ether copolymer of claim 37wherein the copolymer has the formula: ##STR73## where s+t equals (i)the free valence of the ##STR74## moiety and (ii) 4-x; and the averagevalue of t/s+t is about 0.01 to about 0.5.
 55. The linearaminoplast-ether copolymer of claim 38 wherein the copolymer has theformula: ##STR75## where s+t equals (i) the free valence of the##STR76## moiety and (ii) 4-x; and the average value of t/s+t is about0.01 to about 0.5.
 56. The linear aminoplast-ether copolymer of claim 39wherein the copolymer has the formula: ##STR77## where s+t equals (i)the free valence of the ##STR78## moiety and (ii) 4-x.
 57. The linearaminoplast-ether copolymer of claim 40 wherein the copolymer has theformula: ##STR79## where s+t equals (i) the free valence of the##STR80## moiety and (ii) 4-x.
 58. The linear aminoplast-ether copolymerof claim 41 wherein the copolymer has the formula: ##STR81## where s+tequals (i) the free valence of the ##STR82## moiety and (ii) 4-x. 59.The linear aminoplast-ether copolymer of claim 42 wherein the copolymerhas the formula: ##STR83## where s+t equals (i) the free valence of the##STR84## moiety and (ii) 4-x.
 60. The linear aminoplast-ether copolymerof claim 43 wherein the copolymer has the formula: ##STR85## where s+tequals (i) the free valence of the ##STR86## moiety and (ii) 4-x. 61.The linear aminoplast-ether copolymer of claim 1 wherein the copolymerpossesses end groups characterized by a component of the units making upthe copolymer, or a monofunctional group that effectively end-caps thecopolymer, forming the end group.
 62. The linear aminoplast-ethercopolymer of claim 61 wherein the copolymer has the formula: ##STR87##wherein each R₀₀ is the same or different terminal group.
 63. The linearaminoplast-ether copolymer of claim 62 wherein the copolymer has theformula: ##STR88## wherein each R₀₀ is one or more of hydrogen, --R₀₁--H, Amp bonded --(OR)_(p1), --Amp--(OR)_(p1), and anothermonofunctional organic group, and p₁ is a positive number that is equalto the free valence of Amp minus
 1. 64. The linear aminoplast-ethercopolymer of claim 62 wherein the other monofunctional group is one ormore of alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkyoxyalkyl,aroxyalkyl and cycloalkoxyalkyl.
 65. The linear aminoplast-ethercopolymer of claim 62 wherein the copolymer has the formula: ##STR89##where each R₀₀₁ is the same or different, and is R₀₀ or R₀₂ ; R₀₂ is ahydrophobic group, different from RO--, that is covalently bonded to Ampthrough a heteroatom and contains at least two carbon atoms.
 66. Thelinear aminoplast-ether copolymer of claim 62 wherein the copolymer hasthe formula: ##STR90## wherein each R₀₀₂ is one or more of hydrogen,--R₀₁ --H, --(OR)_(p1), --Amp⁰ --(OR)_(p1), or another monofunctionalorganic groups and _(p1) is a positive number that is equal to the freevalence of Amp⁰ minus 1 and Amp⁰ is ##STR91## and x is 0 or
 1. 67. Thelinear aminoplast-ether copolymer of claim 66 wherein the othermonofunctional organic group is one or more of alkyl, cycloalkyl, aryl,alkaryl, aralkyl, alkyoxyalkyl, aroxyalkyl, and cycloalkoxyalkyl. 68.The linear aminoplast-ether copolymer of claim 1 wherein copolymerincludes a minor mole proportion in the repeating structure of thecopolymer of the unit struture:

    --Amp--R.sub.13 --                                         XII,

wherein R₁₃ is the residue of a diol possessing greater hydrophobicitythan R₀₁, thereby providing for a linear copolymer containing thestructure ##STR92## wherein x29 has a value that is greater than x30.69. The linear aminoplast-ether copolymer of claim 68 wherein x30/x29 isless than about
 1. 70. The linear aminoplast-ether copolymer of claim 69wherein x30/x29 is less than about 0.33.
 71. The linear aminoplast-ethercopolymer product of claim 68 wherein R₁₃ is the residue of a diolselected from ##STR93## wherein x31 has a value of about 8 to about 20,x32 has a value of about 23, x33 and x34 have values of 0 to about 8.72. The linear aminoplast-ether copolymer of claim 1 wherein thepolyether compound is a polyethylene oxide diol that possess molecularweights from about 1,000 to about 20,000.
 73. The linearaminoplast-ether copolymer of claim 6 wherein the polyether compound isa polyethylene oxide diol that possess molecular weights from about1,000 to about 20,000.
 74. The linear aminoplast-ether copolymer ofclaim 18 wherein the polyether compound is a polyethylene oxide diolthat possess molecular weights from about 1,000 to about 20,000.
 75. Thelinear aminoplast-ether copolymer of claim 22 wherein the polyethercompound is a polyethylene oxide diol that possess molecular weightsfrom about 1,000 to about 20,000.
 76. The linear aminoplast-ethercopolymer of claim 40 wherein the polyether compound is a polyethyleneoxide diol that possess molecular weights from about 1,000 to about20,000.
 77. The linear aminoplast-ether copolymer of claim 68 whereinthe polyether compound is a polyethylene oxide diol that possessmolecular weights from about 1,000 to about 20,000.
 78. A linearaminoplast-ether copolymer product of a polyfunctional aminoplast with apolyalkylene oxide of the formula:

    H-- Alkylene Oxide --H

where "alkylene oxide" is a divalent moiety containing at least twoalkylene oxide units whether joined or separated, and the terminal Hgroups are active hydrogen, in the presence of an acid catalyst providedin a catalytically effective amount.
 79. The linear aminoplast-ethercopolymer product of claim 78 wherein the aminoplast is one or moreselected form aldehyde reaction prodcuts of melamines, ureas,benzoguanamines and glycolurils.
 80. The linear aminoplast-ethercopolymer product of claim 79 wherein the aminoplast is a glaycoluril.81. The linear aminoplast-ether copolymer product of claim 80 whereinthe aminoplast is the glaycoluril of the formula: ##STR94## where R ishydrogen, alkyl containing 1 to about 4 carbon atoms, and acylcontaining 1 to about 4 carbon atoms, and x is 0 or
 1. 82. Thecopolymerization reaction product of claim 79 wherein the aminoplast isa melamine-aldehyde reaction product.
 83. The copolymerization reactionproduct of claim 79 wherein the aminoplast is a urea-aldehyde reactionproduct.
 84. The copolymerization reaction product of claim 79 whereinthe aminoplast is a benzoguanamine-aldehyde reaction product.
 85. Thelinear aminoplast-ether copolymer product of claim 79 wherein thepolyalkylene oxide has the formula:

    HO--(--CH.sub.2 CH.sub.2 O).sub.x11 CH.sub.2 CH.sub.2 OH   XI,

wherein x11 has a value of about 20 to about
 500. 86. The linearaminoplast-ether copolymer product of claim 85 wherein x11 has a valueof about 50 to about
 350. 87. The linear aminoplast-ether copolymerproduct of claim 86 wherein x11 has a value of about 100 to about 250.88. The linear aminoplast-ether copolymer product of claim 78 whereinthe copolymer contains hydrophobe pendant groups.
 89. The linearaminoplast-ether copolymer product of claim 88 wherein the hydrophobependant groups extend from the aminoplast component of the linearbackbone of the aminoplast-ether copolymer.
 90. The linearaminoplast-ether copolymer product of claim 89 wherein the hydrophobegroups are derived from alcohols, thiols, carboxylic acids,carboxamides, and carbamates.
 91. The linear aminoplast-ether copolymerproduct of claim 89 wherein the hydrophobe groups are derived fromcompounds of the formula: ##STR95## wherein R₀₉ is hydrogen, alkyl of 8to about 24 carbon atoms, alkenyl of 8 to about 24 carbon atoms andalkynyl of 8 to about 24 carbon atoms, R₁₀ is mono, di and tri(aryl),R₁₁ is aryl, mono, di and tri(alkaryl), mono, di and tri(alkcycloalkyl),alkenyl and alkynyl where the alkyl, alkenyl and alkynyl contain 1 toabout 24 carbon atoms and the cycloalkyl contains about 4 to about 8carbon atoms, R₁₂ is one or more alkylene oxide, Y is an active hydrogencontaining group, x13, x14, x15 and x16 are 0 or 1, and two or more ofx13, x14, x15 and x16 have the value of 1 at the same time.
 92. Thelinear aminoplast-ether copolymer of claim 89 wherein the hydrophobegroups are one or more structures of the formulae: ##STR96## and inwhich R₁₄ is hydrogen or alkyl of 1 to about 12 carbon atoms, R₁₅ isaryl or alkyl of 8 to 24 carbon atoms, x17 has a value of 7 to 23, x18has a value of 1 to about 20, x19 has a value of 0 to about 8, x20 is 0or 1, x21 is 0 or 1, x22 has a value of 1 to about 20, x23 has a valueof 1 to about 23, x24 has a value of 0 to about 120, x25 has a value of1 to about 20, x26 has a value of about 8 to about 60, and x27 is 0 or1, the sum of x19 and x20 is 1 to about 23, and the sum of x22 and x25is 1 to about
 20. 93. The linear aminoplast-ether copolymer of claim 89wherein the hydrophobe groups are based on partially saponified fattyacid glycerides.
 94. The linear aminoplast-etlher copolymer of claim 93wherein the partially saponified fatty acid glycerides based hydrophobegroups are derived from partially saponified linseed oil, tall oil,cottonseed oil, castor oil, coconut oil, corn oil, oiticica oil, perillaoil, poppyseed oil, rapeseed oil.
 95. The linear aminoplast-ethercopolymer of claim 93 wherein the hydrophobe groups have one or more ofthe formulae: ##STR97## where R₁₆ are the hydrocarbyl portion of thenatural fatty acid component of the fatty acid glycerides.
 96. Thelinear aminoplast-ether copolymer of claim 93 wherein the hydrophobegroups are ethoxylates of such glycerides having one or more of theformulae: ##STR98## where x28 has a value of 1 to about 200, and R₁₆ arethe fatty acid component of the glyceride.
 97. The linearaminoplast-ether copolymer of claim 78 wherein the polyfunctionalaminoplast is one or more of the aminoplasts of the formulae: ##STR99##wherein R is hydrogen, alkyl containing 1 to about 4 carbon atoms, andacyl containing 1 to about 4 carbon atoms; R₀ is alkyl of from 1 toabout 4 carbon atoms, aryl, cycloalkyl, and the like; R₁ is alkyl offrom 1 to about 4 carbon atoms; and x is 0 or 1, and y is at least 2.98. The linear anoplast-ether copolymer of claim 78 wherein thepolyether compound is a polyethylene oxide diol that is a waterdispersible polyether compound of the formula:

    H.sub.x1 X--(R.sub.04).sub.x4 (R.sub.05).sub.x5 (R.sub.06).sub.x6 (R.sub.07).sub.x7 (R.sub.08).sub.x8 --XH.sub.x2           IX,

wherein X is an active hydrogen-attached functional moiety such as oxy(--O--), sulfidyl (--S--), amino (^(>N--)), carboxy (--COO--),carboxamido, silyl, phosphoryl, and ureido; R₀₄ and R₀₈ are alkyl of 2to about 8 carbon atoms; R₀₅ and R₀₇ are one or more alkylene oxideunits, e.g., such as water dispersible ethylene oxide, propylene oxide,mixed ethylene oxide/1,2-propylene oxide, mixed ethyleneoxide/1,3-propylene oxide, mixed ethylene oxide/1,2-butylene oxide, andmixed ethylene oxide/1,4-butylene oxide; R₀₆ is a divalent group such asalkyleneox, alkylenepolyamine, cycloalkylene polyamine, phenoxy, uriedo,carbamate, and amide; x1 and x2 are each equal to the free valence of X;x3, x4, x5, x6 and x7 are each 0 or 1, and one or more of x4 and x6is
 1. 99. The linear aminoplast-ether copolymer of claim 81 wherein thepolyether compound is a polyethylene oxide diol that is a waterdispersible polyether compound of the formula:

    H.sub.x1 X--(R.sub.04).sub.x4 (R.sub.05).sub.x5 (R.sub.06).sub.x6 (R.sub.07).sub.x7 (R.sub.08).sub.x8 --XH.sub.x2           IX,

wherein X is an active hydrogen-attached functional moiety such as oxy(--O--), sulfidyl (--S--), amino (^(>N--)), carboxy (--COO--),carboxamido, silyl, phosphoryl, and ureido; R₀₄ and R₀₈ are alkyl of 2to about 8 carbon atoms; R₀₅ and R₀₇ are one or more alkylene oxideunits, e.g., such as water dispersible ethylene oxide, propylene oxide,mixed ethylene oxide/1,2-propylene oxide, mixed ethyleneoxide/1,3-propylene oxide, mixed ethylene oxide/1,2-butylene oxide, andmixed ethylene oxide/1,4-butylene oxide; R₀₆ is a divalent group such asalkyleneoxy, alkylenepolyamine, cycloalkylene polyamine, phenoxy,uriedo, carbamate, and amide; x1 and x2 are each equal to the freevalence of X; x3, x4, x5, x6 and x7 are each 0 or 1, and one or more ofx4 and x6 is
 1. 100. The linear aminoplast-ether copolymer of claim 78wherein the polyalkylene oxide is a polyethylene oxide diol that possessmolecular weights from about 1,000 to about 20,000.
 101. The linearaminoplast-ether copolymer of claim 84 wherein the polyalkylene oxide isa polyethylene oxide diol that possess molecular weights from about1,000 to about 20,000.
 102. A method for making a linearaminoplast-ether copolymer which comprises the polymerization reactionof a polyfunctional aminoplast with an ether containing two activehydrogen terminal groups, in the presence of an acid catalyst providedin catalytically effective amounts until the desired molecular weight isachieved.
 103. The method of claim 102 wherein the molecular weight ofthe copolymer ranges from about 12,000 to about 300,000.
 104. The methodof claim 103 wherein the molecular weight of the copolymer ranges fromabout 20,000 to about 100,000.
 105. The method of claim 104 wherein themolecular weight of the copolymer ranges from about 30,000 to about80,000.
 106. The method of claim 102 where in the acid catalyst is aBronsted-Lowery acid.
 107. The method of claim 106 wherein the acidcatalyst is a sulfonic acid.
 108. The method of claim 107 wherein theaminoplast a glycoluril of the formula: ##STR100## where R is hydrogen,alkyl containing 1 to about 4 carbon atoms, and acyl containing 1 toabout 4 carbon atoms, and x is 0 or
 1. 109. The method of claim 108wherein the polyethylene oxide diol has a molecular weight of about8,000.
 110. The method of claim 107 wherein the acid catalyst isdodecylbenzene sulfonic acid.
 111. The method of claim 108 wherein theacid catalyst is dodecylbenzene sulfonic acid.
 112. The method of claim108 wherein there is included a monofunctional hydrophobic reagent. 113.The method of claim 112 wherein the monofunctional hydrophobic reagentis one of an alcohol, thiol, carboxylic acid, carboxamide, and carbamateof the formula: ##STR101## wherein R₀₉ is hydrogen, alkyl of 8 to about24 carbon atoms, alkenyl of 8 to about 24 carbon atoms and alkynyl of 8to about 24 carbon atoms, R₁₀ is mono, di and tri(aryl), R₁₁ is aryl,mono, di and tri(alkaryl), mono, di and tri(alkcycloalkyl), alkenyl andalkynyl where the alkyl, alkenyl and alkynyl contain 1 to about 24carbon atoms and the cycloalkyl contains about 4 to about 8 carbonatoms, R₁₂ is one or more alkylene oxide, Y is an active hydrogencontaining group from one of OH, SH, COOH, CONHR₀₈, and NR₀₉ COOH, x13,x14, x15 and x16 are 0 or 1, and two or more of x13, x14, x15 and x16have the value of 1 at the same time.
 114. The method of claim 113wherein the monofunctional hydrophobic reagent is a mixture ofdodecylphenolethoxylates.
 115. The method of claim 113 wherein themonofunctional hydrophobic reagent is one or more tristyrylphenolethoxylates.